CN104583114B

CN104583114B - The agglomerated thing of the nanowire suspended liquid being stored in container is reduced

Info

Publication number: CN104583114B
Application number: CN201380043732.2A
Authority: CN
Inventors: 迈克尔·尤金·扬; 阿尔琼·丹尼尔·斯里尼瓦斯; 马修·R·罗宾逊
Original assignee: SUZHOU NUOVO FILM Inc
Current assignee: Suzhou Nuovo Film Inc.
Priority date: 2012-06-18
Filing date: 2013-06-18
Publication date: 2017-04-05
Anticipated expiration: 2033-06-18
Also published as: US20130334075A1; EP2861526A1; US20140231282A1; CN104583114A; US20140231281A1; WO2013192232A1; EP2861526A4; JP2015527259A; US8727112B2; KR20150023794A

Abstract

The present invention is disclosed for nano wire storage and the method for shipping and product.A kind of disclosed method includes：A () provides nanowire suspended liquid, which includes the nano wire being suspended in liquid；(b) the nanowire suspended liquid is placed in the container for storing and shipping, suppresses the nano wire from the nanowire suspended liquid to coalesce wherein the container is configured for use in.

Description

The agglomerated thing of the nanowire suspended liquid being stored in container is reduced

The cross reference of related application

Subject application advocates the benefit of the U.S. Provisional Application case the 61/660th, 940 of the submission of on June 18th, 2012, institute The disclosure for stating application case is incorporated herein in entirety by reference.

Technical field

The present invention relates generally to nano wire.It more particularly relates to the agglomerated thing in nanowire suspended liquid subtracts It is few.

Background technology

Nanostructured can bulk material similar with which it is significantly different.Exactly, make efforts to synthesize nano wire to incite somebody to action Its characteristic is used for various applications.

There is the basic skills of two kinds of synthesis nano wires：From up to down with it is bottom-up.In top-down method, lead to The material of larger piece is dwindled into smaller pieces by the technology for crossing such as photoetching process and electrophoresis.In bottom-up method, by into The combination of point atom is synthesizing nano wire.Most of synthetic technology is based on bottom-up method.

A kind of specific bottom-up method is referred to as solution synthesis.In solution synthesis, nano wire can be from including Grow in the reactant mixture of solvent, reagent and template, the reagent includes the material to form the nano wire.With reaction Mixture is heated, and template can be combined with the horizontal plane of crystal of nano wire crystal seed, so induce along substantially perpendicular to The longitudinal direction preferred growth of horizontal plane of crystal.

After synthesis nano wire, the nano wire can be suspended in solvent, and gained suspension can be transferred To in the container for storing and shipping.

For this background, need to research and develop embodiment described herein.

The content of the invention

One aspect of the present invention is related to a kind of method of storage nano line.In one embodiment, methods described includes： A () provides nanowire suspended liquid, which includes the nano wire being suspended in liquid；(b) the nanowire suspended liquid is placed in In container for storage, the nano wire from the nanowire suspended liquid is suppressed to gather wherein the container is configured for use in Knot.

In some embodiments, the headroom of container it is sized for suppress liquid from nanowire suspended liquid Evaporation.In some embodiments, wall of a container has resistance to the nano wire adhesion from nanowire suspended liquid.In some realities Apply in scheme, wall of a container is to having resistance by liquid moistening.In some embodiments, wall of a container is by fluorinated polymer shape Into or be coated with, be selected from a kind of fluorinated polymer of politef, PEP and ETFE. In some embodiments, by the placement of nanowire suspended liquid be in a reservoir synthesize nano wire in the nanowire suspended liquid after Carry out.

In some embodiments, the headroom of container it is sized for suppress liquid from nanowire suspended liquid Evaporation, and wall of a container is to having resistance by liquid moistening.In this kind of embodiment, wall of a container can be by fluorinated polymers Thing is formed or is coated with, such as PEP.

In some embodiments, container includes sized and is formed to mate with the removable of the container internal cross section Piston, and the placement of nanowire suspended liquid is included the nanowire suspended liquid limit is made as in described in the above-described container Volume between moveable piston and the vessel port.In this kind of embodiment, wall of a container can be to by liquid moistening With resistance.

In some embodiments, the headroom of container be sized such that the volume of the headroom with it is described The ratio of total internal volume of container is less than or equal to 10%, e.g., less than or equal to 5%, less than or equal to 4%, be less than or equal to 3%th, less than or equal to 2% or less than or equal to 1%.

In some embodiments, wall of a container is to having resistance, and the wall and the liquid shape by liquid moistening Into contact angle be more than or equal to 90 °, be greater than or equal to 95 °, more than or equal to 100 °, more than or equal to 105 °, be more than Or equal to 110 °, more than or equal to 115 °, more than or equal to 120 °, more than or equal to 125 °, more than or equal to 130 °, more than or Equal to 135 °, more than or equal to 140 °, more than or equal to 145 ° or more than or equal to 150 °.

In some embodiments, the storage period of the nanowire suspended liquid being stored in container is at least 14 days, for example extremely It is few 30 days, at least 60 days, at least 90 days, at least 120 days, at least 150 days, at least 180 days or at least 365 days.

In another embodiment, methods described includes：A () provides nanowire suspended liquid, which includes being suspended in liquid Nano wire；(b) by the nanowire suspended liquid be placed in for storage container in, wherein the wall of a container meet with At least one of lower each：(1) to the nano wire adhesion from the nanowire suspended liquid with resistance；(2) to by institute State liquid moistening and there is resistance.

In some embodiments, wall of a container is formed or be coated with by fluorinated polymer, for example PEP. In some embodiments, the headroom of container is sized evaporates from nanowire suspended liquid for suppression liquid.

Another aspect of the present invention is related to a kind of product.In one embodiment, the product includes：(a) storage container； (b) the nanowire suspended liquid being placed in the storage container, wherein the nanowire suspended liquid includes being suspended in liquid Nano wire, and the storage container be configured for use in suppress from the nanowire suspended liquid nano wire coalesce.

In some embodiments, storage container includes thering is resistance by the nano wire adhesion from nanowire suspended liquid Material formed or the wall that is coated with.In some embodiments, storage container is included by being had by the liquid moistening The wall that the material of resistance is formed or is coated with.In some embodiments, storage container include being formed by fluorinated polymer or The wall being coated with, such as PEP.

In some embodiments, the headroom of storage container is sized for suppressing liquid from nanowire suspended Evaporate in liquid.In some embodiments, storage container is configured with adjustable headroom.In some embodiments, store up Depositing container includes moveable piston that is sized and being formed to mate with the storage container internal cross section, and the nanometer Line suspension is restricted to the volume between the moveable piston and the vessel port.In this kind of embodiment, Storage container can include the wall for being formed or be coated with by fluorinated polymer.

In some embodiments, the headroom of storage container be sized such that the volume of the headroom with The ratio of total internal volume of the storage container is less than or equal to 10%, e.g., less than or equal to 5%, less than or equal to 4%, it is little In or equal to 3%, less than or equal to 2% or be less than or equal to 1%.

In some embodiments, storage container includes the wall to being had resistance by liquid moistening, and the wall and institute The contact angle of liquid formation is stated more than or equal to 90 °, be greater than or equal to 95 °, more than or equal to 100 °, be more than or equal to 105 °, more than or equal to 110 °, more than or equal to 115 °, more than or equal to 120 °, more than or equal to 125 °, be more than or equal to 130 °, more than or equal to 135 °, more than or equal to 140 °, more than or equal to 145 ° or be more than or equal to 150 °.

In some embodiments, the storage period of the nanowire suspended liquid being placed in storage container is at least 14 days, example Such as at least 30 days, at least 60 days, at least 90 days, at least 120 days, at least 150 days, at least 180 days or at least 365 days.

In another embodiment, the product includes：(a) storage container；(b) it is placed in the storage container Nanowire suspended liquid, wherein the nanowire suspended liquid includes the nano wire being suspended in liquid, and the storage container bag Include by meeting the wall that the material of at least one is formed or is coated with the following：(1) to from the nanowire suspended liquid Nano wire adhesion with resistance；(2) to there is resistance by the liquid moistening.

In some embodiments, the wall of storage container is formed or be coated with by fluorinated polymer, for example ethylene fluoride Propylene.In some embodiments, the headroom of storage container it is sized for suppress liquid from nanowire suspended liquid Middle evaporation.In some embodiments, storage container is configured with adjustable headroom.

It is also contemplated by the other side and embodiment of the present invention.Foregoing summary and detailed description below do not mean that Any specific embodiment is limited the invention to, and mean onlys that description some embodiments of the present invention.

Description of the drawings

The property and target of some embodiments for a better understanding of the present invention, should be with reference to being combined in detail below with accompanying drawing Embodiment.

Fig. 1 (a) shows the problem of the nano wire coalescence being stored in container, and Fig. 1 (b) shows reality of the invention Apply the scheme for illustrating certainly described problem.

Fig. 2 shows according to one embodiment of present invention, given in a drop of the surface of solids with placement on said surface Contact angle between liquid.

Fig. 3 (a), Fig. 3 (b) and Fig. 3 (c) show according to one embodiment of present invention, can by adjust inner wall surface can It is moist and produce meniscus of different shapes (liquid meniscus).

Fig. 4 (a) and Fig. 4 (b) shows that according to one embodiment of present invention nano wire is different degrees of with inner wall surface Adhesion,

Fig. 5 shows that according to one embodiment of present invention the another kind of of the nano wire agglomeration problem being stored in container is solved Certainly scheme.

Fig. 6 (a), Fig. 6 (b) and Fig. 6 (c) are the images of the assessment result for showing with being associated in terms of of the invention some.

Fig. 7 (a), Fig. 7 (b) and Fig. 7 (c) are the images of the assessment result for showing with being associated in terms of of the invention some.

Fig. 8 (a), Fig. 8 (b) and Fig. 8 (c) are the images of the assessment result for showing with being associated in terms of of the invention some.

Specific embodiment

Definition

It is defined below suitable for some embodiments of the present invention associated description some in terms of.These definition equally can be with Extend herein.

As used herein, unless the other clear stipulaties of context, otherwise singular references " one (a/an) " and " (the) " Including multiple reference substances.So that it takes up a position, for example, unless the other clear stipulaties of context, otherwise refer to that an object can include Multiple objects.

As used herein, term " group " refers to the set of one or more objects.So that it takes up a position, for example, a group objects can be with Including single object or multiple objects.The object of group can also be referred to as the member of group.The object of group can be with identical or different. Under certain situation, the object of group can share one or more common intrinsics.

As used herein, term " adjacent " refer to close or adjacent to.Adjacent object can be spaced apart from each other or can be each other Reality or directly contact.In some cases, adjacent object can be connected to each other or can be formed integrally with each other.

As used herein, term " substantial " and " about " are for describing and consider small change.When tying with event or situation Close when using, the term may refer to the situation and wherein event or situation are extremely approximate that wherein event or situation clearly occur In situation about occurring.For example, the term is may refer to less than or equal to ± 10%, and e.g., less than or equal to ± 5%, little In or equal to ± 4%, less than or equal to ± 3%, less than or equal to ± 2%, less than or equal to ± 1%, less than or equal to ± 0.5%th, less than or equal to ± 0.1% or less than or equal to ± 0.05%.

As used herein, term " optional " and " optionally " mean that event described later or situation may or can Can not occur, and describe the situation and situation about wherein not occurring occurred including wherein described event or situation.

As used herein, term " adhesion (adhesion/adhere/adhering) " is covered and for a group objects to be deposited on table It is bonded on surface on face, by a group objects, a group objects is absorbed on surface, a group objects is adsorbed onto on surface or is made One group objects is contacted with surface or adjacent with surface.

As used herein, term " nanometer range " or " nm scopes " refer to the size of about 1nm to about 1 micron (μm) (dimension) scope.Nm scopes include " relatively low nm scopes ", " middle nm scopes " and " higher nm scopes ", " the relatively low nm Scope " refers to about 1nm to the size range of about 10nm, and " the middle nm scopes " refers to the size model of about 10nm to about 100nm Enclose, " the higher nm scopes " refers to about 100nm to about 1 μm of size range.

As used herein, term " micrometer range " or " μ m " refer to about 1 μm of size range to about 1 millimeter (mm).μ M scopes include " relatively low μ m ", " middle μ m " and " higher μ m " that " the relatively low μ m " refers to that about 1 μm is arrived About 10 μm of size range, " the middle μ m " refer to about 10 μm to about 100 μm of size range, " the higher μm of model Enclose " refer to about 100 μm of size ranges to about 1mm.

As used herein, term " nanostructured " refers to object of at least one size in nm scopes.Nanostructured can With with any one of various shapes, and can be formed by multiple material.The example of nanostructured includes nano wire, nanometer Pipe and nanoparticle.

As used herein, term " nano wire " refers to the elongated nanostructured for being essentially solid.Generally, the horizontal stroke of nano wire To size (for example, in width, diameter or represent across orthogonal direction meansigma methodss width or diameter form cross sectional dimensions) In nm scopes, longitudinal size (for example, length) is in μ m, and aspect ratio is for about 3 or more than 3.

As used herein, term " nanotube " refers to elongated hollow nanostructures.Generally, the lateral dimension of nanotube (for example, in width, external diameter or represent across orthogonal direction meansigma methodss width or external diameter form cross sectional dimensions) in nm scopes In, longitudinal size (for example, length) is in μ m, and aspect ratio is for about 3 or more than 3.

As used herein, term " nanoparticle " refers to spheroidal nanostructured.Generally, each chi of nanoparticle It is very little (for example, in width, diameter or represent across orthogonal direction meansigma methodss width or diameter form cross sectional dimensions) in nm models In enclosing, and the aspect ratio of the nanoparticle is less than about 3, and such as about 1.

As used herein, term " micrometer structure " refers to object of at least one size in μ m.Generally, micron knot Each size of structure is in μ m or exceeds μ m.Micrometer structure can have any one of various shapes, and can To be formed by multiple material.The example of micrometer structure includes micro wire, micron tube and micron particle.

As used herein, term " micro wire " refers to the elongated micrometer structure for being essentially solid.Generally, the horizontal stroke of micro wire To size (for example, in width, diameter or represent across orthogonal direction meansigma methodss width or diameter form cross sectional dimensions) In μ m, and aspect ratio is for about 3 or more than 3.

As used herein, term " micron tube " refers to elongated hollow micrometer structure.Generally, the lateral dimension of micron tube (for example, in width, external diameter or represent across orthogonal direction meansigma methodss width or external diameter form cross sectional dimensions) in μ m In, and aspect ratio is for about 3 or more than 3.

As used herein, term " micron particle " refers to spheroidal micrometer structure.Generally, each chi of micron particle It is very little (for example, in width, diameter or represent across orthogonal direction meansigma methodss width or diameter form cross sectional dimensions) in a μm model In enclosing, and the aspect ratio of the micron particle is less than about 3, and such as about 1.

The storage of nano wire

Embodiments of the invention are related to reducing or suppressing nanostructure agglomeration thing to store the nano junction while formation Structure.The example of nanostructured includes nano wire, and which can be formed by multiple material, including metal (for example, silver-colored (or Ag), nickel (or Ni), platinum (or Pt), copper (or Cu) and golden (or Au)), quasiconductor (for example, silicon (or Si), indium phosphide (or InP), gallium nitride (or GaN)), optionally doping and transparent conductive oxide and chalcogenide (chalcogenide) (for example, optionally doping and Transparent metal-oxide and chalcogenide), conducting polymer (for example, polyaniline, poly- (acetylene), poly- (pyrroles), poly- (thiophene Fen), poly- (to diphenyl sulfide), poly- (to styrene), poly- (3- alkylthrophenes), polybenzazole, poly- pyrene, polycarbazole, poly- azulene (polyazulene), poly- azepines (polyazepine), poly- (fluorenes), poly- naphthalene, melanin, poly- (3,4- Ethylenedioxy Thiophenes) (or PEDOT), poly- (styrene sulfonate) (or PSS), PEDOT-PSS, PEDOT- polymethylacrylic acid, poly- (3- hexyl thiophenes Fen), poly- (3- octyl thiophenes), poly- (C-61- methyl butyrates) and poly- [2- methoxyl group -5- (2'- ethyls-hexyloxy) -1,4- benzene second Alkene]), insulator (for example, silicon dioxide (SiO₂) and titanium dioxide (or TiO₂)) and its any combinations.Nano wire can have Core-shell structure copolymer is configured or core-many-shell configuration.

Although some embodiments are described in the case of nano wire, can in order to store other types of nanostructured and Implement further embodiment, such as in order to generally elongated and aspect ratio is for about 3 or more than 3 other types of nano junction Structure.Other embodiments can be implemented in order to store micrometer structure, for example in order to generally elongated and aspect ratio be for about 3 or 3 with On micrometer structure.

In certain embodiments, according to solution synthetic reaction forming nano wire.In solution synthetic reaction, nano wire can To grow from the reactant mixture including solvent, reagent and template, the reagent includes the material to form the nano wire. As reactant mixture is heated, template (for example, coverture) can be combined with the horizontal plane of crystal of nano wire crystal seed, together When hinder the growth of horizontal direction, and and then induce along preferentially giving birth to substantially perpendicular to the longitudinal direction of horizontal plane of crystal It is long.One example of solution synthetic reaction is sometimes referred to as used for the polyxol method for producing metal nanometer line, wherein coverture Can be combined with { 100 } surface of 5 times of opposite crystal seed structures, it is allowed to grow on { 111 } surface.The present invention covers other The solution synthetic reaction of type.In addition, the present invention covers the nano wire formed according to Electrospun.

In the case of metal nanometer line, the suitable example containing metal reagent includes slaine, for example silver nitrate (or AgNO₃), silver acetate (or (CH₃COO)₂Ag), silver trifluoroacetate (or (CF₃COO)₂Ag), silver phosphate (or Ag₃PO₄), cross chloric acid Silver (or AgClO₄), cross chloric acid gold (or Au (ClO₄)₃), gold chloride (or HAuCl₄), Palladous chloride. (II) (or PdCl₂), acetyl group Acetone acid palladium (or Pd (C₅H₇O₂)₂), Palladous nitrate. (or Pd (NO₃)₂), tetrachloro palladium (II) acid potassium (or K₂PdCl₄), platinum chloride (II) (or PtCl₂), potassium platinic chloride (or K₂PtCl₆), chloroplatinic acid (or H₂PtCl₆), pentanedione acid platinum (or Pt (C₅H₇O₂)₂) With its any combinations.The example of suitable template (also sometimes referred to as " coverture ") includes polyvinylpyrrolidone, poly- virtue Base amide, polyacrylic acid and its any combinations or copolymer.The example of suitable solvent include wherein containing metal reagent, template and Any other reactant or additive are respectively provided with sufficiently soluble polar solvent.In addition, solvent can serve as reducing agent to incite somebody to action Its corresponding element metallic forms is converted into containing metal reagent.Generally, reproducibility solvent includes at least two hydroxyl of per molecule.Properly The example of reproducibility solvent include glycol, polyhydric alcohol, ethylene glycol or its mixture.More specifically, reproducibility solvent can be with Be for example ethylene glycol, 1,2- Propylene Glycol, 1,3- Propylene Glycol, glycerol (glycerin), glycerol (glycerol), glucose or its What combines.Present invention also contemplates that hydrophobic solvent is used, such as non-polar solven.Other additive or reactant can be included With the uniformity for increasing yield and promoting nanometer line morphology, such as+2 or the iron salt of+trivalent (include ferric acetate, iron chloride, second Acyl group acetone acid ferrum), Sodium Chloride (or NaCl), platinum chloride (or PtCl₂), Palladous chloride. (or PdCl₂), quaternary ammonium salt (for example, bromination Cetyltrimethyl ammonium) and other salt or ionic additive.

After solution synthetic reaction is carried out, non-purified product that can be with purification in the reaction.Specifically, may be used So that other Component seperations of synthesized nano wire and reactant mixture, and be subsequently redispersed in suitable solvent or other With the nanowire suspended liquid of formation in liquid.Nanowire suspended liquid can also be allocated as coating composition or composition for ink.

The example of suitable redispersion solvent include alcohol, water, hydrocarbon (for example, paraffin, halogenated hydrocarbon and cycloaliphatic hydrocarbon), alkene, Alkynes, ketone, ether and its combination.For example, nano wire can be redispersed in isopropanol, methanol, ethanol, water or its combination. Other instantiations of suitable solvent include 2- methyltetrahydrofurans, chlorohydrocarbon, fluorohydrocarbon, acetaldehyde, acetic acid, acetic anhydride, acetone, Acetonitrile, aniline, benzene, benzonitrile, benzyl alcohol, methyl phenyl ethers anisole, butanol, butanone, butyl acetate, butyl ether, butyl formate, butyraldehyde, butanoic acid, Butyronitrile, Carbon bisulfide, carbon tetrachloride, chlorobenzene, chlorobutane, chloroform, hexamethylene, Hexalin, Ketocyclopentane, cyclopentyl methyl ether, double third Keto-alcohol, dichloroethanes, dichloromethane, diethyl carbonate, ether, diethylene glycol, diethylene glycol dimethyl ether, diisopropylamine, diformazan Epoxide ethane, dimethylformamide, dimethyl sulfoxide, dimethylamine, dimethylbutane, dimethyl ether, dimethylformamide, dimethyl-penten Alkane, dimethyl sulfoxide, diox, 12 fluoro- 1-heptanols, ethanol, ethyl acetate, ether, Ethyl formate, ethyl propionate, dichloride Ethylene, ethylene glycol, Methanamide, formic acid, glycerol, heptane, hexafluoroisopropanol, hexamethyl phosphoramide, hexamethylphosphorictriamide, oneself Alkane, hexanone, hydrogen peroxide, hypochlorite, isobutyl acetate, isobutanol, Tetryl formate., isobutyl amine, isobutyltrimethylmethane., isopropyl acetate Ester, diisopropyl ether, isopropanol, 2-aminopropane., ketone peroxide, methanol and calcium chloride solution, methyl cellosolve, methyl acetate, methyl second Base ketone, methyl formate, methyl butyl, methyl n-pro-pyl ketone, methyl tert-butyl ether, dichloromethane, methylene, methyl hexane, first Base pentane, mineral oil, meta-xylene, n-butyl alcohol, n-decane, normal hexane, Nitrobenzol, nitroethane, nitromethane, nitro third Alkane, METHYLPYRROLIDONE, normal propyl alcohol, octafluoro -1- amylalcohols, octane, pentane, pentanone, petroleum ether, phenol, propanol, propionic aldehyde, Propanoic acid, propionitrile, propyl acetate, propyl ether, propyl formate, propylamine, xylol, pyridine, pyrrolidine, sodium hydroxide, containing sodium solution, The tert-butyl alcohol (t-butanol), the tert-butyl alcohol (t-butyl alcohol), t-butyl methyl ether, sym-tetrachloroethane, C3-Fluoroalcohol., tetrahydrochysene furan Mutter, naphthane, toluene, triethylamine, trifluoroacetic acid, trifluoroethanol, trifluoropropanol, triptane, trimethyl cyclohexane, trimethyl Pentane, valeronitrile, dimethylbenzene, xylenols and other similar compounds or solution and its any combinations.

More generally, redispersion solvent can include water, solion or contain solion, ionic liquid, You Jirong Agent (for example, polar organic solvent；Non-polar organic solvent；Aprotic solvent；Proton solvent；Polar non-solute or polarity Proton solvent)；Inorganic solvent or its any combinations.Oil can also be considered as suitable solvent.

After once nano wire redispersion and in being suspended in suitable solvent or other liquid, the nanowire suspended liquid of gained can be with It is transferred in the container for disposing, storing and ship.When nanowire suspended liquid is stored in by glass or other similar material shapes Into container in when, during storage and shipment tend to form nano wire agglomerated thing in this kind of suspension.In nano silver wire In the case of, for example, the nano silver wire for being stored in higher concentration when nano silver wire suspension is (for example,>Under 10mg/mL) When, agglomerated thing is formed and is especially aggravated.Not by particular theory of operation constraint in the case of, this effect may at least in part by Limit in the solubility close to or up silver in isopropanol or other liquid and produce.In addition, as nano silver wire is suspending Concentration in liquid increases, and the interaction between nano wire may play larger effect in suspension flow body dynamics.For receiving The object of meter level, it may be considered that random collision (the sometimes referred to as brownian fluctuations power (Brownian with solvent molecule Fluctuating Force)).In the suspension of dense (crowded), there may be along the length of nano wire uneven Solvent molecule bag, which may cause the uneven brown force along nanowire length, and therefore cause torque.In suspension each other The rotation of close some nano wires may result in the beam of nano wire, stranded or " Bird's Nest ".These beams in the solution may It is more unstable than indivedual lines, and then be settled out from suspension and be deposited on wall of a container or bottom.Also do not receiving specific behaviour In the case of making theoretical constraint, the coalescence of nano wire is produced because of other mechanism, and for example nano wire is first on the wall Begin deposition, and then nano wire is deposited on the nano wire for having deposited in addition, produces the nano wire in agglomerated thing form and tangles.

After nano wire tangles as agglomerated thing, it is impossible to easily retrieve the nano wire.This has higher in nano wire It is particularly problematic when aspect ratio or longer growth, and the obvious phase compared with nanoparticle or other spheroidal nanostructureds Instead.Different from nanoparticle, the nano wire of coalescence is likely difficult to separation and returns to scattered nano wire, because other stirring, grinding Mill or or even ultrasonic Treatment deteriorate may coalescence, or or even destroy individual nanowires or be allowed to fragmentation.The nanometer of coalescence Line effectively may be adhered on wall of a container, and can represent that useful materials are lost during storage and shipment.Coalescence Nano wire is likely to form coagulation block and stabilization removal, and precipitates from suspension, and which may subsequently block coating or print Brush mechanism, causes the striped or other visual defects in coating, and hinders uniformity, relatively low turbidity and the height of gained thin film Transparency.

Embodiments in accordance with the present invention, coalescing from the nano wire of the suspension being stored in container can be by suppress The mode that agglomerated thing is formed stores the nanowire suspended liquid and is reduced or suppresses.Some embodiments of the present invention implement suppression The technology that system is adhered on chamber wall from the nano wire agglomerated thing of suspension or precipitates from suspension.In some embodiments In, evaporated from suspension by suppressing solvent or other liquid, by suppressing chamber wall by solvent or other liquid moistenings, led to Cross and suppress nano wire and any combinations of chamber wall adhesion or these technologies to carry out storage nano line suspension.

Fig. 1 (a) shows the problem of nano wire coalescence, and Fig. 1 (b) shows the solution according to embodiments of the present invention Certainly scheme.As shown in Fig. 1 (a), suspension includes the nano wire 120a being scattered in solvent 110a, and suspension placement In container 100a (such as vial).Although bottle cap 150a is fixed on container 100a, the evaporation of solvent 110a can be Carry out in headroom 140a above suspension meniscus.In the case of relatively large headroom, can carry out substantially The evaporation of degree, reaches the degree that the solvent 110a parts adjacent with meniscus is evaporated from suspension.As shown in Fig. 1 (a), this One evaporation leaves the nano wire 130a for being adhered on the wall 155a of container 100a and tangling as agglomerated thing.

As shown in Fig. 1 (b), a solution of this problem is the headroom of suitably sizing container 100b 140b is controlling the degree that solvent 110b is evaporated from nano wire 120b suspensions.Specifically, by making container 100b sizes Change or shape (for example, become jug contrast wide mouthed bottle), by with being enough to reduce the suspension liquid of remaining headroom 140b Accumulate filling container 100b or its combination to reduce the headroom 140b of container 100b.By reducing headroom 140b, suppress The evaporation of solvent 110b, and then suppress the wall 155a of nano wire 120b and container 100b to adhere.

In some embodiments, the sizing volume and container that can cause headroom 140b of headroom 140b The ratio (being expressed as percentage ratio) of total internal volume (for example, the total capacity of container 100b) of 100b can be less than or equal to about 10%, e.g., less than or equal to about 5%, less than or equal to about 4%, less than or equal to about 3%, it is less than or equal to about 2% or little In or be equal to about 1%, and it is little to about 0.5%, it is little to about 0.1%, it is little to about 0.05% or or even little to about 0%.At some In embodiment, the sizing width that can cause container 100b neck portions of headroom 140b is in container 100b main parts Point width ratio (being expressed as percentage ratio) can less than or equal to about 70%, e.g., less than or equal to about 65%, less than or wait In about 60%, less than or equal to about 55%, less than or equal to about 50%, less than or equal to about 45% or less than or equal to about 40%, and it is little to about 30%, it is little to about 25%, it is little to about 20% or less than 20%.In some embodiments, can retain Limited (even if relatively small) volume of headroom 140b is experiencing during storage and shipment in nano wire 120b suspensions Its thermal expansion is allowed during representative temperature excursion.

Or, or the sizing combination with headroom 140b, can be by the bottle cap 150b of container 100b be configured to Substantially antiseep is reducing the evaporation degree of solvent 110b.Bottle cap 150b may be embodied as such as lid, its can by The screw thread that formed in neck portion and optionally one group sealing ring are being fixed in the neck portion of container 100b.Seepage test One instance interpretation is as follows.The water or other Liquid-filled containers 100b of certain volume can be used.Subsequently, can be turned with specified Square value is screwed to bottle cap 150b in the neck portion of container 100b.Can be with inverted container 100b, so that water covers cervical region portion Divide the abutment with bottle cap 150b.Suitable air pressure (for example, 2psig) can be applied and continue for some time (for example, 2 minutes). After release pressure, bottle cap 150b can be removed and checked.If substantially not finding water on bottle cap 150b or screw thread, So can determine that container 100b is antiseep.In order to further reduce evaporation degree, bottle cap 150b, container can be surrounded The neck portion of 100b, the main part of container 100b or its any combinations wind belt or thin film.

Another kind of solution of nano wire agglomeration problem be dispensing containers 100b with suppress the wall 155b of container 100b by Solvent 110b moistenings, suppression nano wire 120b and wall 155b adhesions or both.In some embodiments, the wall of container 100b 155b can by by solvent 110b moistenings have resistance, to from suspension nano wire 120b adhesion with resistance or its two The material of person is formed or is coated with.In some embodiments, it is possible to use certain material come form or be coated with wall 155b with The combination of resist wet and antisticking characteristic is provided.In other embodiments, it is possible to use combination of different materials being formed or It is coated with wall 155b to provide the combination of resist wet and antisticking characteristic.For given container 100b, the similar solution of the problem Scheme properly select solvent 110b so that the solvent 110b have avoid or reduces with formed or coating wall 155b The tendency of material.

As it would be appreciated, moistening or wettability typically refer to liquid maintains or avoids the tendency contacted with the surface of solids, Which is produced due to the intermolecular interaction when making liquid together with the surface of solids.The degree of moistening can be by adhesion Determining, wherein the adhesion strength between liquid and the surface of solids can cause drop across surface to dynamic balance between power and cohesiveness Sprawl, and the cohesiveness in liquid can cause drop balling-up pearl and avoid contacting with surface.Wettable tolerance It is the contact angle between the surface of solids and placement given liquid of a drop on said surface.As shown in Fig. 2 of the invention Embodiment, contact angle (θ) are angles residing when liquid-gas interface (liquid-vapor interface) is intersected with solid-liquid interface Degree.In this embodiment, a drop of liquid 201 is placed on the surface of solids 202.As liquid 201 is spread on the surface of solids 202 Tendency increase, contact angle reduce.Conversely, the tendency spread over liquid 201 on the surface of solids 202 reduces, contact angle increases Plus.Therefore, contact angle provides the contrary tolerance of moistening.Contact angle (low contact angle) less than 90 ° is indicated generally at moistened surface is Favourable (high moistening), and liquid will tend to sprawl on the surface.Contact angle (high contact angle) more than or equal to 90 ° leads to The often moistening of indication surface is unfavorable (low moistening), and liquid will tend to avoid or reduce contact with surface and formed Compact drop.

Referring back to Fig. 1 (b), can be used for being formed or Application container 100b wall 155b suitable anti-wettability material bag Contact angle is included more than or equal to 90 °, be greater than or equal to about 95 °, greater than or equal to about 100 °, greater than or equal to about 105 °, Greater than or equal to about 110 °, greater than or equal to about 115 °, greater than or equal to about 120 °, greater than or equal to about 125 °, more than or wait In about 130 °, greater than or equal to about 135 °, greater than or equal to about 140 °, greater than or equal to about 145 ° or greater than or equal to about 150 °, and be up to about 160 °, be up to about 170 °, be up to about 175 ° or more than 175 ° those materials.This kind of contact angle can be with Specified for given liquid, such as being wherein suspended with the solvent 110b of nano wire 120b.

For solving the problems, such as nano wire coalescence, various benefits can be provided using anti-wettability material.For example, And refer to Fig. 1 (b), when container 100b is inclined during disposal or shipment, stirred or otherwise move, partial suspended Liquid may be shifted and may be sprawled along the wall 155b of container 100b.Due to the low wetting property of inner wall surface, solvent 110b will Tend to avoid or reduce with the inside-wall surface contact and towards suspension remainder along inner wall surface quickly to downslide It is dynamic, such as with compact drops.When solvent 110b is along wall 155b slide downwards, nano wire 120b courts together with solvent 110b Transport to suspension remainder, and then reduce the nano wire 120b for remaining on wall 155b and tangling as agglomerated thing.

Used as another example, the low wetting property of inner wall surface can affect the shape of meniscus to suppress nano wire to gather Knot.Fig. 3 (a), Fig. 3 (b) and Fig. 3 (c) displayings according to one embodiment of present invention, can be by regulation inner wall surface wettabilitys The meniscus of different shapes for producing.Specifically, Fig. 3 (a) shows the situation of high moistening inner wall surface, wherein because liquid edge Wall 355a is sprawled upward, therefore meniscus is presented spill, and Fig. 3 (b) shows the situation of medium moistening inner wall surface, wherein meniscus The relatively flat adjacent with wall 355b or flat shape is presented, and Fig. 3 (c) shows the situation of low moistening inner wall surface, wherein because Reduce and contact with wall 355c by moving away from wall 355c for liquid, meniscus is presented convex.In the high moistening feelings of Fig. 3 (a) In border, liquid increases by 355 surface area of wall that may be contacted with nano wire 320a along sprawling for wall 355c, and therefore increases Nano wire 320a is adhered to the probability on wall 355a, such as in the case where evaporation occurs.Contrast with this, for Fig. 3's (c) Low moistening situation, liquid reduce the wall 355c surface areas that may be contacted with nano wire 320c away from shifting for wall 355c, and because This reduces the probability of nano wire 320c and wall 355c adhesions.

Or, or combined with the impact of surface wettability, nano wire can receive inner wall surface with adhering for inner wall surface Surface chemical reaction affects.For example, glass and similar material may have dangling bonds, and which is typically referred in component atoms Less than full price number.In the case where being not intended to be fettered by particular theory of operation, the presence of this kind of dangling bonds in inner wall surface can be with Promote the inner wall surface and the chemical interaction between the nano wire of suspension, and then increase nano wire and inwall table The probability of face adhesion.In the case of even substantially can there is no evaporation in this kind of nano wire adhesion and or even in essence On do not exist accommodate nanowire suspended liquid container lean, stirring or other movement in the case of occur.Fig. 4 (a) shows by glass The situation of the wall 455a of the nano wire 420a adhesions that glass or another kind of similar material are formed, and Fig. 4 (b) displayings are by block resistance The situation of the downtrod wall 455b of nano wire 420b adhesions that material is formed.

The example of suitable anti-wettability and block resistance material includes fluorinated polymer (or fluoropolymer), for example, have The polymer based on fluorine carbon of carbon-fluorine bond.The strength and stability of carbon-fluorine bond contributes to the anti-wettability of fluorinated polymer, low Viscosity and low frictional property, and be created substantially absent dangling bonds and contribute to antisticking property of the fluorinated polymer to nano wire. Fluorinated polymer can with fully fluorinated, such as in the polymer wherein based on correspondence hydrocarbon all operational carbon-hydrogen links by carbon- Fluorine bond is replaced, or can with partially fluorinated, such as in the polymer wherein based on correspondence hydrocarbon the subset of operational carbon-hydrogen link by Carbon-fluorine bond is replaced.Fluorinated polymer can be the homopolymer for including a type of monomeric unit, or can be include one kind with The copolymer of the monomeric unit of upper type.

The example of suitable fluorinated polymer includes：

(1) polyvinyl fluoride (or PVF), which can be expressed as：

(2) polyvinylidene fluoride (or PVDF), which can be expressed as：

(3) politef (or PTFE), which can be expressed as：

(4) polychlorotrifluoroethylene (or PCTFE or PTFCE), which can be expressed as：

(5) perfluoroalkoxy (or PFA), which can be expressed as：

(6) PEP (or FEP), which can be expressed as：

(7) ETFE (or poly- (ethylene -co- tetrafluoroethene) or ETFE), which can be expressed as：

(8) ethylene chlorotrifluoroethylene (or poly- (ethylene -co- chlorotrifluoroethylene) or ECTFE), which can be expressed as：

(9) perfluorinated sulfonic acid (or PFSA)

(10) PFPE (or PFPE)

(11) fluorine carbon (chlorotrifluoroethylene vinylidene) (or FPM/FKM)

(12) perfluorinated elastomers (Perfluoroelastomer) (or FFPM/FFKM)

(13) perfluor polyoxy is for Tetramethylene.

(14) combination in aforementioned fluorinated polymer more than both or both.

The other example of suitable anti-wettability and block resistance material includes that density is more than or equal to 0.941g/cm³'s High density polyethylene (HDPE)；Inorganic polymer, such as polymer based on silicon；Super hydrophobic material；Super hydrophilic material；With its combination.

Referring back to Fig. 1 (b), in some embodiments, substantial all inner wall surface of container 100b can be by fluorine Fluidized polymer is formed or is coated with.For the cost that reduces be associated using fluorinated polymer, (which is probably other non-fluorine Change the several times of material cost), a part of of container 100b inner wall surface can be formed by fluorinated polymer or be coated with.Lift For example, corresponding to the wall 155b parts of container 100b main parts and neck portion lower half, (which is more likely outstanding with nano wire Supernatant liquid is contacted) can be formed by fluorinated polymer or be coated with, and the remainder of wall 155b can be gathered by glass, nonfluorinated Compound or other non-fluorinated materials are formed or are coated with.As another example, around curved liquid in container 100b neck portions Wall 155b parts (which is more likely contacted with some nano wires 120b in the case of evaporation) in face can be by fluorinated polymer shape Into or be coated with, and the remainder of wall 155b can be formed by glass, nonfluorinated polymers or other non-fluorinated materials or It is coated with.Optionally, bottle cap 150b can also be formed by fluorinated polymer or is coated with.

Embodiments in accordance with the present invention, another kind of solution of nano wire agglomeration problem show in Figure 5.Here is implemented In example, container 500 is configured to similar to syringe to provide adjustable headroom.Specifically, container 500 includes Jing Sizing and the moveable piston 560 for being formed to mate with 500 internal cross section of container, and by nano wire 520 in solvent 510 Suspension be limited in piston 560 and container 500 opening 570 between volume.The movement of piston 560 can make suspension Shift towards opening 570, so that headroom is reduced and substantially eliminated, and then suppress solvent 510 to evaporate from suspension.

In order to further suppress nano wire to coalesce, the wall 555 of container 500 can by by 510 moistening of solvent have resistance, The material of the adhesion with resistance or both of nano wire 520 is formed or be coated with.For example, the note shown in Fig. 5 The wall 555 of emitter type container 500 can be formed by fluorinated polymer or is coated with.

By according to techniques described herein come storage nano line, it is possible to obtain various benefits.In some embodiments In, the nano wire of high aspect ratio, greater depth and small diameter can experience long-term placement, while receiving described in reduction or suppression The agglomerated thing of rice noodle is formed.In some embodiments, the nano wire of higher concentration can experience long-term placement, at the same reduce or The agglomerated thing of the nano wire is suppressed to be formed.

For example in the middle of nano wire (for example, nano silver wire), in the suspension being stored in container, at least about 30% nano wire (for example, in terms of number) can have at least about 50 aspect ratio, and for example, at least about 35%, at least about 40%th, at least about 45%, at least about 50%, at least about 55%, at least about 60%, at least about 65% or at least about 60%, and It is up to about 80%, is up to about 90% or more than 90%.In some embodiments, at least about 25% nano wire is (for example, with number Mesh meter) can have at least about 100 aspect ratio, for example, at least about 30%, at least about 35%, at least about 40%, at least about 45%th, at least about 50%, at least about 55%, at least about 60% or at least about 65%, and be up to about 75%, be up to about 85% or More than 85%.In other embodiments, at least about 20% nano wire (for example, in terms of number) can have at least about 200 Aspect ratio, for example, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, at least about 50%th, at least about 55% or at least about 60%, and be up to about 70%, be up to about 80% or more than 80%.In other embodiment party In case, at least about 20% nano wire (for example, in terms of number) can have at least about 400 aspect ratio, for example, at least about 25%th, at least about 30%, at least about 35%, at least about 40%, at least about 45%, at least about 50%, at least about 55% or at least About 60%, and be up to about 70%, be up to about 80% or more than 80%.

In the middle of another example, the nano wire (for example, nano silver wire) in suspension, at least about 30% nanometer Line (for example, in terms of number) can have at least about 10 μm of length, for example, at least about 35%, at least about 40%, at least about 45%th, at least about 50%, at least about 55%, at least about 60%, at least about 65% or at least about 60%, and be up to about 80%, It is up to about 90% or more than 90%.In some embodiments, at least about 25% nano wire (for example, in terms of number) can have Have at least about 20 μm of length, for example, at least about 30%, at least about 35%, at least about 40%, at least about 45%, at least about 50%th, at least about 55%, at least about 60% or at least about 65%, and be up to about 75%, be up to about 85% or more than 85%. In other embodiments, at least about 20% nano wire (for example, in terms of number) can have at least about 30 μm of length, for example At least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, at least about 50%, at least about 55% Or at least about, and be up to about 70%, be up to about 80% or more than 80%.

In the middle of another example, the nano wire (for example, nano silver wire) in suspension, at least about 30% nanometer Line (for example, in terms of number) can have equal to or less than about 100nm diameter, for example, at least about 35%, at least about 40%, extremely Few about 45%, at least about 50%, at least about 55%, at least about 60%, at least about 65% or at least about 60%, and be up to about 80%th, it is up to about 90% or more than 90%.In some embodiments, at least about 25% nano wire (for example, in terms of number) Can have equal to or less than about 60nm diameter, for example, at least about 30%, at least about 35%, at least about 40%, at least about 45%th, at least about 50%, at least about 55%, at least about 60% or at least about 65%, and be up to about 75%, be up to about 85% or More than 85%.In other embodiments, at least about 20% nano wire (for example, in terms of number) can have and be equal to or less than The diameter of about 40nm, for example, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, at least About 50%, at least about 55% or at least about 60%, and be up to about 70%, be up to about 80% or more than 80%.

Used as another example, concentration of the nano wire in suspension can be about 4mg/mL or more than 4mg/mL, for example About 5mg/mL or more than 5mg/mL, about 6mg/mL or more than 6mg/mL, about 7mg/mL or more than 7mg/mL, about 8mg/mL or 8mg/ More than mL, about 9mg/mL or more than 9mg/mL, about 10mg/mL or more than 10mg/mL, about 11mg/mL or more than 11mg/mL, or 12mg/mL or more than 12mg/mL, and be up to about 15mg/mL, be up to about 16mg/mL or more than 16mg/mL.

Formed by reducing or suppressing agglomerated thing, the storage period of the nanowire suspended liquid being stored in container can extend, Storage period can be at least about 14 days, at least about 30 days, at least about 60 days, at least about 90 days, at least about 120 days, at least about 150 My god, at least about 180 days, at least about 210 days, at least about 240 days or at least about 365 days, and be up to about 390 days, be up to about 420 It or more than 420 days.In some embodiments, the storage period of nanowire suspended liquid can with regard to Jing corresponding to storage period time Section and characterized for the agglomerated thing formation degree that is maintained in acceptable level.Agglomerated thing forms degree can be according to following Combinations more than any one of test or wherein both or both is characterizing：

(1) after a period of time is stored in container, holding can be measured and is scattered in suspension and (or example can be passed through Such as gentle agitation redispersion) nano wire concentration, such as using optical technology.For example, nano silver wire is in suspension Concentration can be measured to the optical absorption in visible ray (or vis) part by electromagnetic spectrum ultraviolet (or UV).Nano wire Concentration (sample taken out from suspension) in suspension can be by measuring optical density determining, and the optical density can be with Measured by making light be transmitted through suspension along specific direction and determining the decay of light.Light may decline mainly due to scattering Subtract, although being likely to be related to some absorptions.Measured decay can compared with initial decay measured value, or can with it is known The attenuation measurements of the suspension of nano wire concentration compare.Jing after for a period of time, if the reduction of nano wire concentration be less than or Equal to about the 10% of original nanowire concentration, e.g., less than or equal to about 9%, less than or equal to about 8%, less than or equal to about 7%th, less than or equal to about 6%, less than or equal to about 5%, less than or equal to about 4%, less than or equal to about 3%, less than or wait In about 2% or less than or equal to about 1%, then it is considered that it is acceptable that the agglomerated thing in suspension forms degree.

(2) the nano wire amount being adhered on chamber wall can be measured after a period of time is stored in container, for example, is led to Cross and pull down the wall or by suitable chemical treatment.It is also contemplated that the nanometer precipitated with coagulation block form in this kind of assessment Line.For example, the weight of the nano silver wire being adhered on chamber wall, and the silver with placement in the above-described container can be measured Nano wire initial weight compares, and the initial weight can be according to the first of such as original nanowire concentration and nanowire suspended liquid Initial body accumulates to estimate.Jing after for a period of time, if the weight of adhered nano silver wire is less than or equal to nano silver wire initial weight About 10%, e.g., less than or equal to about 9%, less than or equal to about 8%, less than or equal to about 7%, less than or equal to about 6%, Less than or equal to about 5%, less than or equal to about 4%, less than or equal to about 3%, less than or equal to about 2% or less than or equal to about 1%, then it is considered that it is acceptable that the agglomerated thing in suspension forms degree.

(3) after being stored in container for a period of time, it is possible to use the fineness of grinding gauge (grind gauge) is come The presence of any agglomerated thing and size in measurement suspension.As it would be appreciated, the fineness of grinding gauge generally includes depth Variable groove.Top corresponding to groove deepest part, and the agglomerated thing of each size presence and number can pass through Which is determined along the position of the groove.Agglomerated thing can be visible in the form of point defect or striped.For striped, position can be with It is recorded as the part that the section start of striped, i.e. striped advise top closest to fineness.

The agglomerated thing number of measured each size can be with the reference agglomerated thing size distribution phase of acceptable suspension Compare to determine whether discussed suspension is acceptable.It should be noted that can depend on reference to specifying for agglomerated thing size distribution In the specific coating of nanowire suspended liquid.In some embodiments, following steps can be passed through with reference to agglomerated thing size distribution To specify：The agglomerated thing size distribution of different nanowire suspended liquid is measured, the suspension used in required coating is (for example, Form the coating or thin film of transparency conductive electrode), analyze the coating result to determine whether result has acceptable quality, And the agglomerated thing size distribution is associated with the outcome quality obtained using the suspension.

For example, the reference agglomerated thing size distribution for some acceptable suspensions for coating can be appointed as：a) The agglomerated thing that for about 100 μm or more than 100 μm of size is less than 3, less than 2, less than 1 or does not exist；B) size is for about 90 μ More than m or 90 μm of agglomerated thing is less than 3, less than 2, less than 1 or does not exist；C) size is for about 80 μm or more than 80 μm Agglomerated thing is less than 3, less than 2, less than 1 or does not exist；D) agglomerated thing of for about 70 μm or more than 70 μm of size is less than 3rd, less than 2, less than 1 or do not exist；E) size be for about 60 μm or more than 60 μm of agglomerated thing be less than 3, less than 2, no Exist more than 1 or not；F) size is for about that 50 μm or more than 50 μm of agglomerated thing is less than 3, less than 2, less than 1 or does not deposit ；G) size is for about that 40 μm or more than 40 μm of agglomerated thing is less than 3, less than 2, less than 1 or does not exist；Or it is h) aforementioned in Combinations more than both or both.

(4) after being stored in container for a period of time, the nanowire suspended liquid used in required coating is (for example, Form the coating or thin film of transparency conductive electrode), and the result of the coating can be analyzed can to determine whether result has The quality of acceptance.For example, by the suspension of nano silver wire storage a period of time, and transparent leading can be subsequently used for forming of The coating or thin film of electrode.Can measure in turbidity, absorbance and sheet resistance the value of any one or combination, and with it is right Reference value is answered to compare, such as compared with the nano silver wire suspension before storage.Jing after for a period of time, if turbidity, In absorbance and sheet resistance, pact ± 10% of the difference of the value of any one or combination less than or equal to correspondence reference value, such as little In or equal to about ± 9%, less than or equal to about ± 8%, less than or equal to about ± 7%, less than or equal to about ± 6%, less than or Equal to about ± 5%, less than or equal to about ± 4%, less than or equal to about ± 3%, less than or equal to about ± 2% or it is less than or equal to About ± 1%, then it is considered that it is acceptable that the agglomerated thing in the suspension for being discussed forms degree.

Other embodiments

Techniques described herein have in the case of nanostructured is stored nanostructured dispose other side can Application.Specifically, nanowire suspended liquid may become more unstable when shearing force is undergone.Shearing force can be to nano wire Apply torque, and the rotation of approximating some nano wires which may be caused to bundle is most of irreversible to be formed Agglomerated thing.Therefore, nanowire suspended liquid is transmitted or is transferred in container or transmits from container or be transferred out of to reduce and cut Shear force is allowed to minimize.

In order to reduce shearing force, fluid transmission or transfer assembly (such as pipe, pipeline, pipet etc.) can be by low viscosity Formed or be coated with, such as above-mentioned fluorinated polymer with low-friction material.Furthermore it is possible to select the size of fluid transmitting assembly Or shape is further to reduce shearing force, for example, nanowire suspended liquid is transferred to by using the larger pipe of cross-sectional diameter It is transferred out of in container or from container.In addition it is possible to use low-shear pump, such as lobe pump (lobe pump), internal gear pump and Screw pump (progressive cavity pump).In addition, coating apparatus and associated component (such as channel mould) can be by low viscosity Formed or be coated with, such as above-mentioned fluorinated polymer with low-friction material.

Example

Following instance describes the specific aspect of some embodiments of the invention, to illustrate to one of ordinary skill in the art With offer description.Example should not be construed as the restriction present invention, because the example is only provided suitable for understanding and putting into practice the present invention The concrete grammar of some embodiments.

Nano silver wire suspension is stored in different types of bottle, and assesses the agglomerated thing of the bottle and form journey Degree.Fig. 6 (a) show be vibrate in vial after about 1 minute when the nano silver wire that is suspended in isopropanol (or IPA).Such as Seen in Fig. 6 (a), suspension does not carry out obvious mistake profit (de-wetting) in inner wall surface.Fig. 6 (b) is illustrated in vibration Afterwards about 2 hours when same containers in nano silver wire in IPA.Suspension in the headroom big portion as IPA evaporates Drying, and nano wire agglomerated thing is divided to be adhered in inner wall surface.Fig. 6 (c) show be store about 2 weeks in vial after Nano silver wire in IPA.Substantially coalescence is seen on inwall glass surface.

Comparatively speaking, Fig. 7 (a) show be vibrate in perfluoroalkoxy (or PFA) bottle after about 20 seconds when it is outstanding Float on the nano silver wire in IPA.As seen in Fig. 7 (a), suspension loses in inner wall surface and moistens.Fig. 7 (b) shows after shaking Nano silver wire when about 1 minute in same containers in IPA.The most of mistake in inner wall surface of suspension in headroom is moistened.Fig. 7 (c) show be store about 2 weeks in PFA bottles after nano silver wire in IPA.Nano silver wire has been directed towards the sedimentation of PFA bottom of bottle portion. IPA has been evaporated in headroom, and is seen a small amount of coalescence and be adhered in inner wall surface.

Compare as another, Fig. 8 (a) show be vibrate in PEP (or FEP) bottle after about 10 seconds when The nano silver wire being suspended in IPA.As seen in Fig. 8 (a), suspension loses in inner wall surface and moistens.Fig. 8 (b) is illustrated in vibration Afterwards about 30 seconds when same containers in nano silver wire in IPA.Compared with PFA surfaces, the suspension in headroom is with very fast Speed substantially loses profit in inner wall surface.Fig. 8 (c) show be store about 2 weeks in FEP bottles after nano silver wire in IPA.Silver Nano wire has been directed towards the sedimentation of FEP bottom of bottle portion.During IPA has been evaporated to headroom and it is condensed into beadlet, and sees few Or coalescence is adhered in inner wall surface.

From assessment, determine that nano silver wire tends to be adhered in glass bottle wall rather than in FEP bottle walls.When nano silver wire in When suspension in alcohol experiences long-term placement in vial, nano wire is found as alcohol evaporates and is adhered in glass bottle wall, But when the suspension with same composition is similarly stored in FEP bottles, observe few adhesion with wall or without adhesion. In the case of not fettered by particular theory of operation, compared with the surface wettability of glass, the relatively low table of fluorinated polymer The reason for face wettability is probably difference between observed FEP and vial.In addition, according to assessment, PFA shows and glass Less, but more compared with FEP to a certain extent nano silver wires adhesion is compared, especially in the nano silver wire of higher concentration Under.

Although the present invention is described by reference to its specific embodiment, those skilled in the art will appreciate that, can To carry out various changes simultaneously in the case of without departing from true spirit of the present invention as defined by the appended patent claims and scope Replace equivalent.Furthermore it is possible to carry out various modifications so that particular condition, material, material composition, method or process are adapted to this The target of invention, spirit and scope.All such modification is intended to belong in this scope of the appended claims.Definitely Say, although the method disclosed herein is described by reference to the specific operation carried out with particular order, it should be appreciated that these Operation can be combined in the case of without departing from teachings of this disclosure content, divide again or reorder to form equivalent method.Cause This, unless be explicitly indicated herein, the order for otherwise operating and packet do not limit the present invention.

Claims

1. a kind of method of storage nano line, which includes：

Nanowire suspended liquid is provided, which includes the nano wire being suspended in liquid；With

By the nanowire suspended liquid be placed in for storage container in, wherein the container be configured for use in suppression from The nano wire coalescence of the nanowire suspended liquid, the headroom of the container are designed to the body of the headroom of the container Product is less than or equal to 10% with the ratio of total internal volume of container, for suppressing the liquid to steam from the nanowire suspended liquid Send out.

2. method according to claim 1, wherein the wall of a container is to the nano wire from the nanowire suspended liquid Adhesion is with resistance.

3. method according to claim 1, wherein the wall of a container is to having resistance by the liquid moistening.

4. method according to claim 1, wherein the wall of a container is formed or be coated with by fluorinated polymer.

5. method according to claim 4, wherein the fluorinated polymer is selected from politef, PEP And ETFE.

6. method according to claim 4, wherein the fluorinated polymer is PEP.

7. method according to claim 1, wherein the container includes being formed to mate with the container internal cross section Moveable piston, and the nanowire suspended liquid placement is included being made as the nanowire suspended liquid limit in the above-described container Volume between the moveable piston and the vessel port.

8. method according to claim 7, wherein the wall of a container is to having resistance by the liquid moistening.

9. method according to claim 1, wherein it is institute by the nanowire suspended liquid placement to be in the above-described container Carry out after synthesizing the nano wire in stating nanowire suspended liquid.

10. a kind of method of storage nano line, which includes：

The nanowire suspended liquid is placed in the container for storage, wherein the wall of a container is met in the following At least one：(1) to the nano wire adhesion from the nanowire suspended liquid with resistance；(2) to by the liquid moistening With resistance, the headroom of the container is designed to the volume of the headroom of the container and total internal volume of container Ratio be less than or equal to 10%, for suppressing the liquid to evaporate from the nanowire suspended liquid.

11. methods according to claim 10, wherein the wall of the container is formed or applied with which by fluorinated polymer Cloth.

12. methods according to claim 11, wherein the fluorinated polymer is PEP.

A kind of 13. products, which includes：

Storage container；With

The nanowire suspended liquid being placed in the storage container, wherein the nanowire suspended liquid includes being suspended in liquid Nano wire, and the storage container is configured for use in the nano wire coalescence suppressed from the nanowire suspended liquid, it is described The headroom of container is designed to the volume of the headroom of the container and the ratio of total internal volume of container is less than or waits In 10%, for suppressing the liquid to evaporate from the nanowire suspended liquid.

14. products according to claim 13, wherein the storage container is included by from the nanowire suspended liquid Nano wire material of the adhesion with resistance formed or the wall that is coated with.

15. products according to claim 13, wherein the storage container is included by anti-to being had by the liquid moistening Property material formed or the wall that is coated with.

16. products according to claim 13, wherein the storage container includes being formed by fluorinated polymer or applied with which The wall of cloth.

17. products according to claim 16, wherein the fluorinated polymer is PEP.

18. products according to claim 13, wherein the storage container is configured with adjustable headroom.

19. products according to claim 18, wherein the storage container includes being formed to mate with the storage container The moveable piston of cross section, and the nanowire suspended liquid is restricted to open with the container in the moveable piston Volume between mouthful.

20. products according to claim 19, wherein the storage container includes being formed by fluorinated polymer or applied with which The wall of cloth.

A kind of 21. products, which includes：

Storage container；With

The nanowire suspended liquid being placed in the storage container, wherein the nanowire suspended liquid includes being suspended in liquid Nano wire, and the storage container includes by meeting the wall that the material of at least one is formed or is coated with the following： (1) to the nano wire adhesion from the nanowire suspended liquid with resistance；(2) to there is resistance by the liquid moistening, The headroom of the container is designed to the volume of the headroom of the container and the ratio of total internal volume of container is less than Or 10% is equal to, for suppressing the liquid to evaporate from the nanowire suspended liquid.

22. products according to claim 21, wherein the wall of the storage container is formed or used by fluorinated polymer Its coating.

23. products according to claim 22, wherein the fluorinated polymer is PEP.

24. products according to claim 21, wherein the storage container is configured with adjustable headroom.